Glyceride oxidation inhibited by 5-pentadecyl resorcinol



Patented Aug. 31, 1948 GLYCEBIDE OXIDATION INHIBITED BY S-PENTADECYL RESORCINOL Harry M. Barnes, Summit, N. J., assignor to General Foods Corporation, Hoboken, N. 1., a corporation of Delaware No Drawing. Application October 17, 1944, Serial No. 559,135

12 Claims. 1

The present invention relates to the stabilization of organic materials subject to oxidative deterioration.

An object of the invention is to provide a process for stabilizing organic materials, such as certain essential oils, animal and vegetable oils and fats, cereals and other foodstufis containing such oils or fats, against oxidative deterioration.

Another object of the invention is to provide novel compositions of organic materials subject to oxidative deterioration and a. compound which is effective to stabilize the organic materials against said deterioration.

These and other objects will be more readily understood from the following specific description.

It is well known that certain essential oils, vegetable and animal oils and fats, cereals and other foodstuffs containing these oils and fats undergo certain chemical changes when exposed to air or other oxidative influences, resulting in changes of color, odor, or other properties which render them objectionable or unusable. The treatment of essential oils and materials contalning them, forms the subject-matter of my divisional application Serial No. 787,482, filed November 21, 1947.

According to this invention, I have found that these organic materials subject to oxidative deterioration can be stabilized by the addition of very small amounts of S-pentadecyl resorcinol,

'decyl resorcinol had gained somewhat less in body weight than the control animals who had not been receiving S-pentadeciil resorcinol. However, the loss in body weight was parallel to the reduction in the total food intake. At the conclusion of the test, the animals were chloroiormed, and autopsy revealed the absence of any abnormal organic condition.

5-pentadecyl resorcinol is entirely suitable for use in accordance with the invention. It does not At the impart any taste, color or odor to the organic materials to which it is added and is furthermore suitable for addition to foodstuffs. In protecting the materials of the type described against oxidation it is advantageous to-make use of 'an. antioxidant that is readily and substantially o ilsolu.-

ble. This is especially true of foodstuffs containing oils in dispersion inasmuch as an antioxidant dissolved in the oil will be at the locus of oxidation. S-pentadecyl resorcinol fulfills the condition of oil-solubility and is, furthermore, insoluble in water so thatit remains in the oil at anproducts or incorporated by mechanical mixing into substantially dry and granular oil.or fat containing materials such as cereals, or it may be dissolved in an oil or fat carrier and the admixture stirred in or sprayed upon the material to be protected.

The concentrations of 5-pentadecyl resorcinol necessary will depend upon the materials to which it is added and the length of time during which antioxidative protection is desired. In general, I have found that satisfactory results are obtained using concentrations ranging from 0.01 per cent to 0.50 per cent.

By the term "animal and vegetable oils and fats" I mean those oils and fats which are of animal or vegetable origin and are glycerides of the more or less unsaturated higher fatty acids mixed with some saturated glycerides. Some of such materials are fish oils, lard, beef tallow, olive oil, coconut oil, and peanut oil. By essential oils I mean those volatile oils of characteristic odor derived from plants, leaves, flowers, fruits, etc., such as oil of bitter almonds and lemon oil.

Further embodiments of my invention will appear from the more detailed description set forth below, it being understood, however, that this mor detailed description is given by way of iilustration and explanation only, and not by way of limitation, since various changes therein may be made by those skilled in the art without departing from the scope and spirit of the present invention.

EXAMPLE I Samples of a food product composed of wheat farina, wheat germ and corn flour were pulveraide in a mortar, thoroughly mixed with 0.20% o! 5-pentadecyl resorcinol and then placed in closed bottles and stored at 113 1". A sample containing no 5-pentadecy1 resoroinol was similarly prepared. The samples were tested periodically for the onset of rancidity. Results of the tests follow.

TABLI: I

Per cent oi o-pentadecyl resorcinol relative to food to dwalo product 9 Per cent Dow EXANIPLE II.

Tun: II

- Per cent of B-penta- Time required decyl resorcinol relaior rancidity tive to food product to develop Per can: Days 0. 00 28 0. 06

EXAMPLE 11:

Samples of pulverized corn grits were prepared containing 0.20 per cent and 0.02 per cent -pentadecyl resorcinol. With each sample was mixed 9. material known to facilitate rancidity development in the corn grits. The resulting mixtures were placed in screw-cap glass jars and incubated at 113 F. A control sample containing no antioxidant was similarly prepared and treated. The results appear in the following table.

Tam: 111

Per cent of 5-penta- Time required decyl resorcinol relafor rancidity tive to corn grits to develop Per cent Du I 0.00 Less t an 1 0. 02 6 0. 2] 48 EXAMPLE IV Samples of processed corn flour were similarly treated and tested as in Example III. The results follow:

Teens IV Per cent of 5-penta- 'Iime required deeyl resorcinol relafor rancid ity tive to corn flour to develop Per cent Days 0. 00 l 0. 02 3 0. 70

The results shown in Examples I, II, III and IV clearly indicate the eflicacy of B-pentadecyl resorcinol as an antioxidant when added in small quantities to oil-containing vegetable products.

EXAMPLEV Batches or a 25 per cent aqueous solution of gelatin were homogenized with approximately 10% of oil of bitter almonds, to which varying amounts of 5-pentadecy1 resorcinol were added. The resulting mixture was poured into trays in a layer about one-quarter inch thick, and dried rapidly to-minimize oxidation. The dried product was cut into slabs, pulverized to 40-80 mesh, placed in wide-mouthed open bottles and stored at 100 F. for three weeks. A control sample without 5-pentadecyl resorcinol was similarly prepared. The amounts of oil of bitter almonds remaining after the drying and grinding process and after the three weeks storage period were determined. The following table records the resuits.

Team: V

Per cent oi oil oi bitter Per cent of almonds remaining delcyil risorcgnol re a ve o o o bitter almonds Aiter drying g x and grinding Per cent Per cent Per cent EXAIVIPLE VI Lemon oil was mixed with gelatin and treated substantially as in Example V. The following table records the percentage of lemon oil remain- It is evident from the results recorded in Tables V and'VI that the losses sustained by oxidative deterioration of flavoring materials during processing and storage may be markedly decreased by the use of small quantities of 5-pentadecyl resorcinol.

EXAMPLE VII A sample of lard was stabilized by dissolving therein 0.20% 5-pentadecyi resorcinoi by weight. The eifectiveness of the 5-pentadecyl resorcinol as an oxidation inhibitor was measured in an accelerated oxidation test at C. in a Barcroit- Warburg oxygen absorption apparatus. As a control an untreated portion of the same lard was similarly tested. The induction period" reported in the table is the elapsed time from the start of the oxidation test until exidence of rancidity was observed.

TABLE VII Induction period of treated fat EXAMPLE VIII Wheat farina, flaked wheat germ, tricalcium phosphate, sugar, salt, dried yeast, reduced iron, malt syrup and water were thoroughly mixed into a dough and a solution of 5-pentadecyl resorcinol in coconut oil was added. The added 5- pentadecyl resorcinol constituted 0.05% of the mass. The resulting dough was cooked in an autoclave and thereafter was shredded and dried. The dried Product was ground fine and part of the powder was held in vacuo at room temperature for 16 hours while the remainderwas toasted minutes at 150 C. in an electric oven. Samples of the evacuated material and of the toasted material (adjusted to 3.5% moisture). were incubated at 45 C. and observed over a period of time for evidence of rancidity. A control sample prepared with the same amount of added coconut oil but no S-pentadecyl resorcinol was treated in the same way and observed for rancidity.

The results of the observations are set out in the following table.

TABLE VIII Antioxidant cooked into dough Days to go Rancid at 45 C.

Antioxidant Untoasted, 16 Hrs. in Vacuo at Room Temperature Toasted and Ad usted to 3.6 a Moisture 0.05'7 fi-pentadecyl resorcinol 47 54 condor 27 4 27 It will be apparent from the foregoing that the invention is capable of many other variations particularly with respect to the organic materials which are stabilized and the manner of incorporating the 5-pentadecyl resorcinol in the materials, without departing from the essential features of the invention.

What I claim is:

1. A process for stabilizing a material selected from the group consisting of animal and vegetable oils and fats containing a glyceride of an unsaturated higher fatty acid against oxidative deterioration which comprises adding thereto a small effective amount of S-pentadecyl resorcinol.

2. A process for stabilizing a material selected from the grou consisting of animal and vegetable oils and fats containing a glyceride of an unsaturated higher fatty acid against oxidative deterioration which comprises adding thereto 5- pentadecyl resorcinol in a quantity of about 0.01 to about 0.50 per cent. by weight of said material.

3. A process for stabilizing a, material containing a glyceride of an unsaturated higher fatty acid against oxidative deterioration which comprises adding thereto 5-pentadecy1 resorcinol in a quantity of about 0.01 to about 0.50 per cent.

by weight of said material.

4. A process for stabilizing a. cereal foodstuff containing a glyceride of an unsaturated higher fatty acid against oxidative deterioration which comprises incorporating in said foodstuff a small effective amount of 5-pentadecyl resorcinol.

5. A process for preparing a cooked cereal foodstufi' which comprises preparing a dough of a cereal foodstuff containing a. glyceride of an unsaturated higher fatty acid, incorporatin into said dough a small effective amount of S-Dentadecyl resorcinol, and thereafter cooking the dough.

6. A composition stabilized against oxidative deterioration comprising a material selected from the group consisting of animal and vegetable oils and fats containing a glyceride of an unsaturated higher fatty acid and a small amount of 5-pentadecyl resorcinol present therein as a stabilizer.

7. A composition stabilized against oxidative deterioration comprising a material selected from the group consisting of animal and vegetable oils and fats containing a, glyceride of an unsaturated higher fatty acid and 5-pentadecyl resorcinol present therein as a stabilizer in a quantity of about 0.01 to about 0.50 per cent. by weight of said material.

8. A composition stabilized against oxidative deterioration comprising a material containing a glyceride of an unsaturated higher fatty acid and a small amount of 5-pentadecyl resorcinol present therein as a. stabilizer.

9.A composition stabilized against oxidative deterioration comprising a material containing a lyceride of an unsaturated higher fatty acid and from about 0.01 to about 0.50 per cent. by weight 5-pentadecyl resorcinol present therein as a stabilizer.

10. A composition stabilized against oxidative deterioration comprising a cereal foodstuff containing a glyceride of an unsaturated higher fatty acid and a small quantity of 5-pentadecyi resorcinolpresent therein as a. stabilizer.

11. A process of stabilizing a material containing a glyceride of an unsaturated higher fatty acid against oxidative deterioration which comprises adding thereto a small effective amount of S-pentadecyl resorcinol.

12. A composition stabilized against oxidative deterioration comprisin a cooked cereal food stufi containing a'glyceride of an unsaturated higher fatty acid and a small quantity of 5- pentadecyl resorcinol therein a: a stabilizer.

HARRY M. BARNES.

BWEBENCES CITED The following references are of record in the file of-this patent:

UNITED STATES PATENTS Number Name Date 2,031,069 Richardson Feb. 18, 1936 2,031,930 Buc Feb. 25, 1936 2,047,355 Borden July 14, 1936 2,131,904 Salzberg Oct. 4, 1938 2,282,810 Musher May 12, 1942 

